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Dalí Atomicus, by Philippe Halsman. Taken in 1948, way before Photoshop was created. It reportedly took 28 attemps until the photographer gets satisfied with the result. In this image you can see the wires suspending the easel and the painting and the assistant hands on the chair, those elements were later removed for the final version.
Update: Time has a small piece about this picture, narrated by the photographer’s daughter. The video shows another amazing Dalí portraits by Halsman, as well as some of the failed attemps.